U.S. patent number 5,681,806 [Application Number 08/590,711] was granted by the patent office on 1997-10-28 for dryer-activated fabric conditioning compositions containing uncomplexed cyclodextrin.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Helen Bernardo Tordil, Toan Trinh.
United States Patent |
5,681,806 |
Trinh , et al. |
October 28, 1997 |
Dryer-activated fabric conditioning compositions containing
uncomplexed cyclodextrin
Abstract
An effective amount of uncomplexed cyclodextrin, in the form of
particles having particle sizes below about 5 microns, is
incorporated into solid dryer-activated fabric conditioning
compositions which are used in dryers to treat fabrics. The
cyclodextrin is thereby attached to the fabrics and subsequently
provides effective control of odors when they come in contact with
the treated fabric. The fabric conditioning compositions can be
attached to substrates to prepare an article of manufacture or be
in the form of detergent compatible particles, for use with
conventional laundry detergents.
Inventors: |
Trinh; Toan (Maineville,
OH), Tordil; Helen Bernardo (West Chester, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
21912461 |
Appl.
No.: |
08/590,711 |
Filed: |
January 24, 1996 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
278703 |
Jul 21, 1994 |
|
|
|
|
40703 |
Mar 31, 1993 |
|
|
|
|
Current U.S.
Class: |
510/330; 510/441;
510/470; 510/504; 510/515; 510/520 |
Current CPC
Class: |
C11D
3/001 (20130101); C11D 3/222 (20130101); C11D
3/505 (20130101); C11D 17/047 (20130101) |
Current International
Class: |
C11D
3/50 (20060101); C11D 3/00 (20060101); C11D
3/22 (20060101); C11D 17/04 (20060101); C11D
001/62 (); C11D 003/22 () |
Field of
Search: |
;510/519,521,515,516,518,504,499,470,505,441,330,520 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
124452 |
|
Jul 1983 |
|
JP |
|
128973 |
|
Jun 1986 |
|
JP |
|
63-164953 |
|
Jul 1988 |
|
JP |
|
64-15049 |
|
Jan 1989 |
|
JP |
|
3-170415 |
|
Jul 1991 |
|
JP |
|
Other References
H Hashimoto, "Application of Cyclodextrins to Foods, Toiletries and
Other Products in Japan," (1988) pp. 1-12. .
H. Hashimoto, "Studies on the Industrial Production and Application
of Cyclodextrins," Denpun Kagaku, vol. 36, No. 1 pp. 35-42 (1-15)
(1989)..
|
Primary Examiner: Lieberman; Paul
Assistant Examiner: Hardee; John R.
Attorney, Agent or Firm: Aylor; Robert B.
Parent Case Text
This application is a file wrapper continuation of our application
Ser. No. 08/278,703, filed Jul. 21, 1994, now abandoned which is a
file wrapper continuation of our application Ser. No. 08/040,703,
filed Mar. 31, 1993, now abandoned.
Claims
What is claimed is:
1. Solid, dryer-activated fabric conditioning composition
comprising from about 10% to about 95% of fabric softening agent
selected from cationic and nonionic fabric softeners and mixtures
thereof and an effective amount, sufficient to absorb and control
odor of uncomplexed cyclodextrin having a particle size of less
than about 5 microns, said fabric treatment composition being
flowable at dryer operating temperatures.
2. The composition of claim 1 wherein said cyclodextrin is selected
from the group consisting of: unsubstituted cyclodextrins
containing from about six to about twelve glucose units;
derivatives of said unsubstituted cyclodextrins; and mixtures
thereof, and wherein said cyclodextrin is capable of forming
inclusion complexes with odor compounds.
3. The composition of claim 2 wherein at least a major portion of
said cyclodextrin is selected from the group consisting of
alpha-cyclodextrin; beta-cyclodextrin; gamma-cyclodextrin; and
mixtures thereof.
4. The composition of claim 3 wherein at least a major portion of
said cyclodextrin is beta-cyclodextrin.
5. The composition of claim 4 additionally containing an effective
amount of an inclusion complex of said beta-cyclodextrin and
perfume.
6. The composition of claim 5 wherein at least a major portion of
said perfume is selected from the group consisting of: highly
volatile perfume having boiling points of about 250.degree. C. or
lower; moderately volatile perfume having boiling points of from
about 250.degree. C. to about 300.degree. C.; and mixtures
thereof.
7. The composition of claim 6 wherein at least a major portion of
said perfume is highly volatile perfume.
8. The composition of claim 1 wherein at least a major portion of
said particle size is from about 0.001 microns to about 5
microns.
9. The composition of claim 8 wherein said cyclodextrin complex has
a majority of particles ranging in size between about 0.05 micron
to about 5 microns.
10. The composition of claim 8 wherein said cyclodextrin is
selected from the group consisting of: alpha-cyclodextrin;
beta-cyclodextrin; gamma-cyclodextrin; and mixtures thereof.
11. The composition of claim 10 wherein at least a major portion of
said cyclodextrin is beta-cyclodextrin.
12. A granular detergent composition comprising an effective amount
of detergent compatible particles which survive the wash and adhere
to fabric surfaces, said particles comprising at least about 10%
and less than about 95% of fabric softening agent and an effective
amount of uncomplexed cyclodextrin having a particle size of less
than about 5 microns.
13. The method of treating fabrics to provide odor control
comprising adding the composition of claim 1 to an automatic
laundry dryer with a bundle of wet fabrics.
14. The method of claim 13 wherein said fabrics are flat woven
fabrics.
Description
TECHNICAL FIELD
The present invention relates to an improvement in dryer activated,
e.g., dryer-added, fabric conditioning (softening) products and/or
compositions, said products, and/or compositions, being,
preferably, either in particulate form; compounded with other
materials in solid form, e.g., tablets, pellets, agglomerates,
etc.; or attached to a substrate.
BACKGROUND OF THE INVENTION
The use of cyclodextrin as a complexing agent for materials is well
documented, including the disclosures in U.S. Pat. No. 4,348,416,
Boden (flavoring material for use in chewing gum, dentifrices,
cosmetics, etc.); U.S. Pat. No. 4,296,138, Boden (similar to U.S.
Pat. No. 4,348,416); U.S. Pat. No. 4,265,779, Gandolfo et al. (suds
suppressors for use in detergent compositions); U.S. Pat. No.
4,547,365, Kubo et al. (cyclodextrin/hair-waving-active complexes);
U.S. Pat. No. 4,548,811, Kubo et al. (waving lotion); U.S. Pat. No.
4,616,008, Hirai et al. (antibacterial complexes); and U.S. Pat.
No. 4,732,759 and U.S. Pat. No. 4,728,510, Shibanai et al.
(complexes of bath additives), all of said patents being
incorporated by reference. Despite the voluminous art relating to
the preparation and use of cyclodextrin complexes in various
products, there has been much less activity relative to the use of
free, uncomplexed cyclodextrin as a material to absorb, e.g.,
odors, out of the air. There has been a disclosure of using free,
uncomplexed cyclodextrin in an aqueous fabric softener composition
(Laid Open Jap. Pat. Appln. 63-165,498, Jul. 8, 1988), but nothing
relative to the use of uncomplexed cyclodextrin in dryer-added
fabric conditioning/softener compositions.
Cyclodextrin actives have been disclosed as set forth in detail in
the patents incorporated by reference herein. However, for
commercial success, the effect must be obtained consistently and
the cost must be commensurate with the benefit obtained. Use of a
large particle size or an aqueous softener composition delivery
system results in insufficient control of odors by cyclodextrin.
There has been no discussion in the art of small particle size
uncomplexed cyclodextrin delivered by a dryer-activated product to
fabric.
SUMMARY OF THE INVENTION
It has now been discovered that free cyclodextrin Incorporated into
solid dryer activated fabric conditioning compositions, especially
those comprising a fabric softening agent, can control odor and
that small particle size cyclodextrin can control odors more
effectively, especially those containing at least an effective
amount of cyclodextrin having a particle size of less than about
12, preferably less than about 10, more preferably less than about
8, and even more preferably less than about 5, typically between
about 0.001 and about 10, preferably between about 0.05 and about 5
microns (micrometers). The small particle cyclodextrins provide a
remarkable and totally unexpected improvement in the control of
malodors, e.g., cigarette odor, when applied from a dryer-activated
fabric softener composition. This odor control was not expected in
view of the prior art. Fabrics which are treated with the small
particle size free cyclodextrin are noticeably less smelly when
they are exposed to air containing malodors.
The advantage of improved odor control is especially important when
the odor is being released from the underarm area and there is
limited time to diminish the odor before it escapes to the air.
When the amount of time available to effect odor control is
limited, small particles are essential to provide the speed of odor
absorption required to give a noticeable effect.
DESCRIPTION OF THE INVENTION
Cyclodextrin can be obtained in small particle form by grinding
larger particles, e.g., those made by normal crystallization
processes to achieve the desired particle size. One can also modify
the crystallization process to affect the size of the precipitated
particles. For any use that requires fast odor control, the
particle size reduction is essential to see the full benefit of the
cyclodextrin. At least an effective amount of the cyclodextrin
should be in small particle form. Effective amounts depend upon the
delivery effectiveness and the end result desired.
1. CYCLODEXTRINS
As used herein, the term "cyclodextrin" (CD) includes any of the
known cyclodextrins such as unsubstituted cyclodextrins containing
from six to twelve glucose units, especially, alpha-, beta-,
gamma-cyclodextrins, and mixtures thereof, and/or their
derivatives, and/or mixtures thereof, that are capable of forming
inclusion complexes with odor materials. Beta-cyclodextrin is the
most preferred cyclodextrin and the one which benefits most from
the small particle size. Alpha-, beta-, and gamma-cyclodextrins can
be obtained from, among others, American Maize-Products Company
(Amaizo), Hammond, Ind.; and Roquette Corporation, Gurnee, Ill.
There are many derivatives of cyclodextrins that are known.
Representative derivatives are those disclosed in U.S. Pat. No.
3,426,011, Parmerter et al., issued Feb. 4, 1969; U.S. Pat. Nos.
3,453,257, 3,453,258, 3,453,259, and 3,453,260, all in the names of
Parmerter et al., and all issued Jul. 1, 1969; U.S. Pat. No.
3,459,731, Gramera et al., issued Aug. 5, 1969; U.S. Pat. No.
3,553,191, Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No.
3,565,887, Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No.
4,535,152, Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No.
4,616,008, Hirai et al., issued Oct. 7, 1986; U.S. Pat. No.
4,638,058, Brandt et al., issued Jan. 20, 1987; U.S. Pat. No.
4,746,734, Tsuchiyama et al., issued May 24, 1988; and U.S. Pat.
No. 4,678,598, Ogino et al., issued Jul. 7, 1987, all of said
patents being incorporated herein by reference. Examples of
cyclodextrin derivatives suitable for use herein are
methyl-.beta.-CD, hydroxyethyl-.beta.-CD, and
hydroxypropyl-.beta.-CD of different degrees of substitution (DS),
available from, among others, Amaizo; Aldrich Chemical Company,
Milwaukee, Wis.; and Wacker Chemicals (USA), New Canaan, Conn.
Water-soluble derivatives are also highly desirable.
The individual cyclodextrins can also be linked together, e.g.,
using multifunctional agents to form oligomers, polymers, etc.
Examples of such materials are available commercially from Amaizo
and from Aldrich Chemical Company (.beta.-CD/epichlorohydrin
copolymers).
It is also desirable to use mixtures of cyclodextrins to provide
odor control for a variety of odor materials. Such mixtures, e.g.,
can provide broader odor control by complexing with a wider range
of odorous materials. Mixtures of cyclodextrins can conveniently be
obtained by using intermediate products from known processes for
the preparation of cyclodextrins including those processes
described in U.S. Pat. No. 3,425,910, Armbruster et al., issued
Feb. 4, 1969; U.S. Pat. No. 3,812,011, Okada et al., issued May 21,
1974; U.S. Pat. No. 4,317,881, Yagi et al., issued Mar. 2, 1982;
U.S. Pat. No. 4,418,144, Okada et al., issued Nov. 29, 1983; and
U.S. Pat. No. 4,738,923, Ammeraal, issued Apr. 19, 1988, all of
said patents being incorporated herein by reference. Preferably at
least a major portion of the cyclodextrins are alpha-cyclodextrin,
beta-cyclodextrin, and/or gamma-cyclodextrin, more preferably
beta-cyclodextrin. Some cyclodextrin mixtures are commercially
available from, e.g., Ensuiko Sugar Refining Company, Yokohama,
Japan.
2. CYCLODEXTRIN PARTICLE SIZES
As used herein, "cyclodextrin" refers to both the free
cyclodextrin, and any optional complexed cyclodextrin that is
present, when particle size is discussed. The particle size of the
cyclodextrins herein are selected to improve the pick-up of odors
and/or the release, and especially the rate-of-release, of any
perfume from a complex.
In the normal production process, the cyclodextrins are isolated
effectively and conveniently by fractional crystallization. This
process normally produces crystalline solids having particle sizes
of about 20 microns or larger. A beta-cyclodextrin sample obtained
from the American Maize-Products Company is composed of about 88%
of cyclodextrin with particle size larger than 20 microns, and with
about 58% of cyclodextrin with particle size in the 49 to 118
micron range, as determined by a Malvern Particle and Droplet
Sizer, Model 2600C, sold by Malvern Instruments, Inc.,
Southborough, Mass. Surface area availability of the uncomplexed
cyclodextrin is essential for effective and efficient odor control
performance by cyclodextrin powder. By way of exemplification, for
particles of essentially the same shape, all particles having the
same exact size, one gram of cyclodextrin of 5 micron size has the
same surface area as 100 g of cyclodextrin of 50 micron size, and 1
g of cyclodextrin of 3 micron size has the same surface area as
1600 g of cyclodextrin of 120 micron size.
The small particles of this invention, e.g., those having a
particle size of less than about 12 microns, preferably less than
about 10 microns, more preferably less than about 8 microns, and
even more preferably less than about 5 microns, are desirable for
providing a quick pickup of odor, or release of perfume, when the
complexes are wetted.
The particle size range is typically between about 0.001 and 10
microns, preferably between about 0.05 and 5 microns. It is highly
desirable that at least an effective amount of the active be in
complexes having the said particle sizes. It is desirable that at
least about 75%, preferably at least about 80% and more preferably
at least about 90% of the complex that is present have the said
particle sizes. It is even better if essentially all of the complex
has the said particle sizes.
These small particles of the invention are conveniently prepared by
mechanical, e.g., grinding techniques. Cyclodextrin, and/or
cyclodextrin complexes, with large particle sizes can be pulverized
to obtain the desired smaller particles of about 10 microns and
less by using, e.g., a fluid energy mill. Examples of fluid energy
mills are the Trost Air Impact Pulverizers, sold by Garlock Inc.,
Plastomer Products, Newtown, Pa.; the Micronizer fluid energy mills
sold by Sturtevant, Inc., Boston, Mass.; and the Spiral Jet Mill
sold by Alpine Division, MicroPul Corporation (Hosokawa Micron
International, Inc.), Summit, N.J. The optional small particle size
cyclodextrin/perfume complex is preferably prepared by mechanical
methods, e.g., kneading a slurry of the cyclodextrin and the
perfume.
As used herein, the particle size refers to the largest dimension
of the particle and to the ultimate (or primary) particles. The
size of these primary particles can be directly determined with
optical or scanning electron microscopes. The slides must be
carefully prepared so that each contains a representative sample of
the bulk cyclodextrin. The particles' sizes can also be measured by
any of the other well-known methods, e.g., wet sieving,
sedimentation, light scattering, etc. A convenient instrument that
can be used to determine the particle size distribution of the dry
cyclodextrin powder directly (without having to make a liquid
suspension or dispersion) is the Malvern Particle and Droplet
Sizer, Model 2600C, sold by Malvern Instruments, Inc.,
Southborough, Mass. Some caution should be observed in that some of
the dry particles may remain agglomerated. The presence of
agglomerates can be further determined by microscopic analysis.
Some other suitable methods for particle size analysis are
described in the article "Selecting a particle size analyzer:
Factors to consider," by Michael Pohl, published in Powder and Bulk
Engineering, Volume 4 (1990), pp: 26-29, incorporated herein by
reference. It is recognized that the very small particles of the
invention can readily aggregate to form loose agglomerates that are
easily broken apart by either some mechanical action or by the
action of water. Accordingly, particles should be measured after
they are broken apart, e.g., by agitation or sonication. The
method, of course, should be selected to accommodate the particle
size and maintain the integrity of the complex particles, with
iterative measurements being made if the original method selected
proves to be inappropriate. Care should be taken to avoid contact
of the cyclodextrin particles with water to prevent premature
dissolution.
3. THE COMPOSITIONS
The present invention also relates to improved solid
dryer-activated fabric softener compositions which are either (A)
incorporated into articles of manufacture in which the compositions
containing the small particle cyclodextrin are, e.g., on a
substrate, or, are (B) in the form of particles (including, where
appropriate, agglomerates, pellets, and tablets of said particles).
Such compositions contain from about 10% to about 95% of fabric
softening agent and at least an effective amount of said small
particle size cyclodextrin.
A. Substrate Articles
In preferred embodiments, the present invention encompasses
articles of manufacture. Representative articles are those that are
adapted for use to provide unique perfume benefits and to soften
fabrics in an automatic laundry dryer, of the types disclosed in
U.S. Pat. No. 3,989,631 Marsan, issued Nov. 2, 1976; U.S. Pat. No.
4,055,248, Marsan, issued Oct. 25, 1977; U.S. Pat. No. 4,073,996,
Bedenk et al., issued Feb. 14, 1978; U.S. Pat. No. 4,022,938, Zaki
et al., issued May 10, 1977; U.S. Pat. No. 4,764,289, Trinh, issued
Aug. 16, 1988; U.S. Pat. No. 4,808,086, Evans et al., issued Feb.
28, 1989; U.S. Pat. No. 4,103,047, Zaki et al., issued Jul. 25,
1978; U.S. Pat. No. 3,736,668, Dillarstone, issued Jun. 5, 1973;
U.S. Pat. No. 3,701,202, Compa et al., issued Oct. 31, 1972; U.S.
Pat. No. 3,634,947, Furgal, issued Jan. 18, 1972; U.S. Pat. No.
3,633,538, Hoeflin, issued Jan. 11, 1972; and U.S. Pat. No.
3,435,537, Rumsey, issued Apr. 1, 1969; and U.S. Pat. No.
4,000,340, Murphy et al., issued Dec. 28, 1976, all of said patents
being incorporated herein by reference.
Typical articles of manufacture of this type include articles
comprising:
I. a fabric conditioning composition comprising:
i. from about 30% to about 95% of normally solid, dryer softenable
material, typically fabric softening agent; and
ii. an effective amount, preferably from about 5% to about 70%, of
uncomplexed particulate cyclodextrin having a particle size of less
than about 12 microns, as described hereinbefore;
iii. optionally, an effective amount, preferably from about 0.5% to
about 60%, of perfume/cyclodextrin complex, as described
hereinafter;
II. a dispensing means which provides for release of an effective
amount of said composition including an effective amount of ii,
sufficient to provide odor control, to fabrics in an automatic
laundry dryer at automatic laundry dryer operating temperatures,
e.g., from about 35.degree. C. to 115.degree. C.
When the dispensing means is a flexible substrate, e.g., in sheet
configuration, the fabric conditioning composition is releasably
affixed on the substrate to provide a weight ratio of conditioning
composition to dry substrate ranging from about 10:1 to about
0.5:1, preferably from about 5:1 to about 1:1. The invention also
comprises the method of manufacturing such an article of
manufacture utilizing said uncomplexed cyclodextrin and optional
complex iii., either by application of the cyclodextrin, and
optional complex iii. directly to said dispensing means II., or by
premixing the cyclodextrin and any complex iii. with the fabric
softening agent i. The softener helps protect the complex from the
water in the environment which is desirable. However, separate
application of cyclodextrin, whether uncomplexed or as a complex,
to said substrate is also possible and can diminish interaction of
softener ingredients with any perfume. The cyclodextrin requires
some material to affix it to the dispensing means, i.e., to
"immobilize" it, said material being "mobilized" by the dryer to
release the uncomplexed cyclodextrin from the dispensing means and
then affix ("immobilize") said uncomplexed cyclodextrin on fabrics
that are being dried.
The term "fabric softening agent" as used herein includes cationic
and nonionic fabric softeners used alone and also in combination
with each other. A preferred fabric softening agent of the present
invention is a mixture of cationic and nonionic fabric
softeners.
(i) Fabric Softening Agents
Examples of fabric softening agents that are especially useful in
the substrate articles are the compositions described in U.S. Pat.
No. 4,103,047, Zaki et al., issued Jul. 25, 1978; U.S. Pat. No.
4,237,155, Kardouche, issued Dec. 2, 1980; U.S. Pat. No. 3,686,025,
Morton, issued Aug. 22, 1972; U.S. Pat. No. 3,899,435, Diery et
al., issued Nov. 19, 1974; and U.S. Pat. No. 4,073,996, Bedenk,
issued Feb. 14, 1978; said patents are hereby incorporated herein
by reference.
Another preferred type of fabric softener is described in detail in
U.S. Pat. No. 4,661,269, Toan Trinh, Errol H. Wahl, Donald M.
Swartley and Ronald L. Hemingway, issued Apr. 28, 1987, said patent
being incorporated herein by reference.
Examples of nonionic fabric softeners are the sorbitan esters,
C.sub.12 -C.sub.26 fatty alcohols, and fatty amines described
herein.
More biodegradable fabric softener compounds can be desirable.
Biodegradability can be increased, e.g., by incorporating easily
destroyed linkages into hydrophobic groups. Such linkages include
ester linkages, amide linkages, and linkages containing
unsaturation and/or hydroxy groups. Examples of such fabric
softeners can be found in U.S. Pat. No. 3,408,361, Hannheimer,
issued Oct. 29, 1968; U.S. Pat. No. 4,709,045, Kubo et al., issued
Nov. 24, 1987; U.S. Pat. No. 4,233,451, Pracht et al., issued Nov.
11, 1980; U.S. Pat. No. 4,127,489, Pracht et al., issued Nov. 28,
1979; U.S. Pat. No. 3,689,424, Berg et al., issued Sep. 5, 1972;
U.S. Pat. No. 4,128,485, Baumann et al., issued Dec. 5, 1978; U.S.
Pat. No. 4,161,604, Elster et al., issued Jul. 17, 1979; U.S. Pat.
No. 4,189,593, Wechsler et al., issued Feb. 19, 1980; and U.S. Pat.
No. 4,339,391, Hoffman et al.; issued Jul. 13, 1982, said patents
being incorporated herein by reference.
A preferred article of the present invention includes a fabric
treatment composition which comprises from about 5% to about 70%,
preferably from about 10% to about 60%, more preferably from about
15% to about 50%, of uncomplexed cyclodextrin ii, as discussed
hereinbefore, and from about 30% to about 95%, preferably from
about 40% to about 90%, of fabric conditioning (softening) agent.
Preferably, said fabric softening agent is selected from cationic
and nonionic fabric softeners and mixtures thereof. Preferably,
said fabric softening agent comprises a mixture of about 5% to
about 95% of a Cationic fabric softener and about 5% to about 95%
of a nonionic fabric softener by weight of said fabric treatment
agent. The selection of the components is such that the resulting
fabric treatment composition has a melting point above about
38.degree. C. and is flowable at dryer operating temperatures.
(ii) Uncomplexed Cyclodextrin
The uncomplexed cyclodextrin is the one discussed hereinbefore in
detail.
(iii) Cyclodextrin/Perfume Complexes
In addition to the uncomplexed cyclodextrins, the products herein
can also contain from about 0.5% to about 60%, preferably from
about 1% to about 50%, cyclodextrin/perfume inclusion complexes as
disclosed in the patents incorporated herein by reference. Perfumes
are highly desirable, can usually benefit from protection, and can
be complexed with cyclodextrin. Fabric softening products typically
contain perfume to provide an olfactory aesthetic benefit and/or to
serve as a signal that the product is effective.
The perfume in such products is often lost before it is needed.
Perfumes can be subject to damage and/or loss by the action of,
e.g., oxygen, light, heat, etc. For example, due to the high energy
input and large air flow in the drying process used in the typical
automatic laundry dryers, a large part of the perfume provided by
dryer-added softener products has been lost out the dryer vent.
Even for less volatile components, as described hereinafter, only a
small fraction remains on the fabrics after the drying cycle. The
loss of the highly volatile fraction of the perfume, as described
hereinafter, is much higher. Usually the loss of the highly
volatile fraction is practically total. Due to this effect, many
perfumes used in, e.g., dryer-added fabric softener compositions,
have been composed mainly of less volatile, high boiling (having
high boiling points), perfume components to maximize survival of
the odor character during storage and use and thus provide better
"substrate substantivity." The main function of a small fraction of
the highly volatile, low boiling (having low boiling points),
perfume components in these perfumes is to improve the fragrance
odor of the product itself, rather than impacting on the treated
fabric. However, some of the volatile, low boiling perfume
ingredients can provide a fresh and clean impression to the fabric,
and it is highly desirable that these ingredients be deposited and
present on the fabric.
The perfume ingredients and compositions of this invention are the
conventional ones known in the art. Selection of any perfume
component, or amount of perfume, is based solely on aesthetic
considerations. Suitable perfume compounds and compositions can be
found in the art including U.S. Pat. No. 4,145,184, Brain and
Cummins, issued Mar. 20, 1979; U.S. Pat. No. 4,209,417, Whyte,
issued Jun. 24, 1980; U.S. Pat. No. 4,515,705, Moeddel, issued May
7, 1985; and U.S. Pat. No. 4,152,272, Young, issued May 1, 1979,
all of said patents being incorporated herein by reference. Many of
the art recognized perfume compositions are relatively substantive,
as described hereinafter, to maximize their odor effect on
substrates. However, it is a special advantage of perfume delivery
via the perfume/cyclodextrin complexes that nonsubstantive perfumes
are also effective.
A substantive perfume is one that contains a sufficient percentage
of substantive perfume materials so that when the perfume is used
at normal levels in products, it deposits a desired odor on the
treated fabric. In general, the degree of substantivity of a
perfume is roughly proportional to the percentage of substantive
perfume material used. Relatively substantive perfumes contain at
least about 1%, preferably at least about 10%, substantive perfume
materials.
Substantive perfume materials are those odorous compounds that
deposit on substrates via the treatment process and are detectable
by people with normal olfactory acuity. Such materials typically
have vapor pressures lower than that of the average perfume
material. Also, they typically have molecular weights of about 200
or above, and are detectable at levels below those of the average
perfume material.
Perfumes can also be classified according to their volatility, as
mentioned hereinbefore. The highly volatile, low boiling, perfume
ingredients typically have boiling points of about 250.degree. C.
or lower. Many of the more moderately volatile perfume ingredients
are also quickly lost. For example, substantially all of such
perfumes are lost in the drying cycle of a typical laundry process.
The moderately volatile perfume ingredients are those having
boiling points of from about 250.degree. C. to about 300.degree. C.
The less volatile, high boiling, perfume ingredients referred to
hereinbefore are those having boiling points of about 300.degree.
C. or higher. A significant portion of even these high boiling
perfume ingredients, considered to be highly substantive, can be
lost, during a laundry drying cycle, and it is desirable to have
means to retain more of these ingredients on the fabrics. Many of
the perfume ingredients as discussed hereinafter, along with their
odor characters, and their physical and chemical properties, such
as boiling point and molecular weight, are given in "Perfume and
Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published
by the author, 1969, incorporated herein by reference.
Examples of the highly volatile, low boiling, perfume ingredients
are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl
formate, iso-bornyl acetate, camphene, cis-citral (neral),
citronellal, citronellol, citronellyl acetate, paracymene, decanal,
dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol,
eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile,
cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool,
linalool oxide, linalyl acetate, linalyl propionate, methyl
anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde,
methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone,
iso-menthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl
acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene,
beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol,
terpinyl acetate, and vertenex (para-tertiary-butyl cyclohexyl
acetate). Some natural oils also contain large percentages of
highly volatile perfume ingredients. For example, lavandin contains
as major components: linalool; linalyl acetate; geraniol; and
citronellol. Lemon oil and orange terpenes both contain about 95%
of d-limonene.
Examples of moderately volatile perfume ingredients are: amyl
cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene,
cedrene, cinnamic alcohol, coumarin, dimethyl benzyl carbinyl
acetate, ethyl vanillin, eugenol, iso-eugenol, flor acetate,
heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial
(para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde),
gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol,
beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl
citrate, vanillin, and veratraldehyde. Cedarwood terpenes are
composed mainly of alpha-cedrene, beta-cedrene, and other C.sub.15
H.sub.24 sesquiterpenes.
Examples of the less volatile, high boiling, perfume ingredients
are: benzophenone, benzyl salicylate, ethylene brassylate,
galaxolide
(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gama-2-benzopyran
), hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl
pentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl
dihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk
ketone, musk tibetene, and phenylethyl phenyl acetate.
Cyclodextrin inclusion complexes (perfume/cyclodextrin, or
perfume/CD, complexes), as described hereinafter, of the high
boiling, the moderately volatile, and the low boiling perfume
ingredients are stable (a) throughout the mixing of the complexes
with the remainder of the compositions, e.g., the molten fabric
softener mixes, especially when the fabric softener mixes contain
some clay, and the coating of the resulting fabric softening
compositions onto flexible substrates to form fabric conditioning
sheets, (b) during the application of the composition to the
substrate, e.g., during the drying of the wet fabrics in tumble
dryers, and (c) during use, e.g., during the wearing of the dry
fabrics. The content of the perfume in the cyclodextrin, e.g.,
.beta.-cyclodextrin, inclusion complex is typically from about 5%
to about 15%, more normally from about 7% to about 12%.
Perfume Complex Formation
The perfume/cyclodextrin inclusion complexes of this invention are
formed in any of the ways known in the art. Typically, the
complexes are formed either by bringing the perfume and the
cyclodextrin together in a suitable solvent, e.g., water, or,
preferably, by kneading/slurrying the ingredients together in the
presence of a suitable, preferably minimal, amount of solvent,
preferably water. The kneading/slurrying method is particularly
desirable because it results in smaller particles so that there is
less, or no, need to reduce the particle size and less solvent is
needed and therefore less separation of the solvent is required.
Other equivalent mechanical processes, e.g., milling, extrusion,
etc., which require only small amounts of water and/or which result
in very small particle sizes are desirable. Disclosures of complex
formation can be found in Atwood, J. L., J. E. D. Davies & D.
D. MacNichol, (Ed.): Inclusion Compounds, Vol. III, Academic Press
(1984), especially Chapter 11; Atwood, J. L. and J. E. D. Davies
(Ed.): Proceedings of the Second International Symposium of
Cyclodextrins Tokyo, Japan, (July, 1984); and J. Szejtli,
Cyclodextrin Technology, Kluwer Academic Publishers (1988). All of
said publications are incorporated herein by reference.
In general, perfume/cyclodextrin complexes have a molar ratio of
perfume compound to cyclodextrin of 1:1. However, the molar ratio
can be either higher or lower, depending on the size of the perfume
compound and the identity of the cyclodextrin compound. The molar
ratio can be determined easily by forming a saturated solution of
the cyclodextrin and adding the perfume to form the complex. In
general the complex will precipitate readily. If not, the complex
can usually be precipitated by the addition of electrolyte, change
of pH, cooling, etc. The complex can then be analyzed to determine
the ratio of perfume to cyclodextrin.
As stated hereinbefore, the actual complexes are determined by the
size of the cavity in the cyclodextrin and the size of the perfume
molecule. Although the normal complex is one molecule of perfume in
one molecule of cyclodextrin, complexes can be formed between one
molecule of perfume and two molecules of cyclodextrin when the
perfume molecule is large and contains two portions that can fit in
the cyclodextrin. Highly desirable complexes can be formed using
mixtures of cyclodextrins since perfumes are normally mixtures of
materials that vary widely in size. It is usually desirable that at
least a majority of the material be alpha-, beta-, and/or
gamma-cyclodextrin, more preferably beta-cyclodextrin.
Continuous complexation operations usually involve the use of
supersaturated solutions, and/or mechanical processing, e.g.,
kneading/slurrying, and/or temperature manipulation, e.g., heating
and then either cooling, freeze-drying, etc. The complexes may be
dried, or not, depending on the next step in the process for making
the desired composition. In general, the fewest possible process
steps are preferred to avoid loss of perfume.
(iv) Dispensing Means
In a preferred substrate article embodiment, the fabric treatment
compositions are provided as an article of manufacture in
combination with a dispensing means such as a flexible substrate
which effectively releases the composition in an automatic laundry
(clothes) dryer. Such dispensing means can be designed for single
usage or for multiple uses. The dispensing means can also be a
"carrier material" that releases the fabric softener composition
and then is dispersed and/or exhausted from the dryer.
The dispensing means will normally carry an effective amount of
fabric treatment composition. Such effective amount typically
provides sufficient fabric conditioning agent and/or anionic
polymeric soil release agent for at least one treatment of a
minimum load in an automatic laundry dryer. Amounts of fabric
treatment composition for multiple uses, e.g., up to about 30, can
be used. Typical amounts for a single article can vary from about
0.25 g to about 100 g, preferably from about 0.5 g to about 20 g,
most preferably from about 1 g to about 10 g.
One such article comprises a sponge material releasably enclosing
enough fabric treatment composition to effectively impart fabric
soil release and softness benefits during several cycles of
clothes. This multi-use article can be made by filling a hollow
sponge with about 20 grams of the fabric treatment composition.
Other devices and articles suitable far dispensing the fabric
treatment composition into automatic dryers include those described
in U.S. Pat. No. 4,103,047, Zaki et al., issued Jul. 25, 1978; U.S.
Pat. No. 3,736,668, Dillarstone, issued Jun. 5, 1973; U.S. Pat. No.
3,701,202, Compa et al., issued Oct. 31, 1972; U.S. Pat. No.
3,634,947, Furgal, issued Jan. 18, 1972; U.S. Pat. No. 3,633,538,
Hoeflin, issued Jan. 11, 1972; and U.S. Pat. No. 3,435,537, Rumsey,
issued Apr. 1, 1969. All of these patents are incorporated herein
by reference.
Highly preferred paper, woven or nonwoven "absorbent" substrates
useful herein are fully disclosed in U.S. Pat. No. 3,686,025,
Morton, issued Aug. 22, 1972, incorporated herein by reference. It
is known that most substances are able to absorb a liquid substance
to some degree; however, the term "absorbent" as used herein, is
intended to mean a substance with an absorbent capacity (i.e., a
parameter representing a substrate's ability to take up and retain
a liquid) from 4 to 12, preferably 5 to 7, times its weight of
water.
(v) Usage
The substrate embodiment of this invention can be used for
imparting the above-described fabric treatment composition to
fabric to provide odor control and/or perfume effects and/or
softening and/or antistatic effects to fabric in an automatic
laundry dryer comprises: commingling pieces of damp fabric by
tumbling said fabric under heat in an automatic clothes dryer with
an effective amount of the fabric treatment composition, at least
the continuous phase of said composition having a melting point
greater than about 35.degree. C. and said composition being
mobilized, e.g., flowable, at dryer operating temperature, said
composition comprising from about 5% to about 70%, preferably from
about 10% to about 60%, more preferably from about 15% to about
50%, of uncomplexed cyclodextrin and, optionally, from about 0.5%
to about 60%, preferably from about 1% to about 50%, more
preferably from about 5% to about 40%, of perfume/cyclodextrin
complex and from about 30% to about 95%, preferably from about 40%
to about 90%, of fabric softening agent selected from the
above-defined cationic and nonionic fabric softeners and mixtures
thereof.
B. Detergent-Compatible Compositions
Another type of dryer activated fabric conditioning composition
useful herein is detergent-compatible and includes compositions
containing softening particles such as those known in the art,
including specifically: U.S. Pat. No. 3,936,537, Baskerville Jr.,
issued Feb. 3, 1976, and U.S. Pat. No. 4,095,946, Jones, issued
Jun. 20, 1978, both of which teach the use of intimate mixtures of
organic dispersion inhibitors (e.g., stearyl alcohol and fatty
sorbitan esters) with solid fabric softener to improve the survival
of the softener in the presence of detergent in the washer so that
the softener can act on the fabrics when it is mobilized in the
dryer, and U.S. Pat. No. 4,234,627, Schilling, issued Nov. 18,
1980, which teaches microencapsulation of fabric softener (The
microcapsules survive the wash and adhere to the fabric surface.
They are then ruptured by subsequent tumbling of the fabric in the
dryer, thereby releasing softener to the fabrics.)
The particles in such detergent-compatible fabric conditioning
compositions comprise at least about 10% of fabric softening agent,
preferably cationic fabric softening agent. For detergent
compatibility, the particles often have a coating as described
herein, a sufficiently large particle size (e.g., a minimum
dimension greater than about 5,000 microns), or some combination of
coating and particle size depending upon the level of protection
desired.
The free cyclodextrin and any optional perfume/cyclodextrin
complexes, as described hereinafter, are incorporated into fabric
conditioning compositions, especially when the compositions are to
be added to laundry detergents. It is believed that when the
perfume/cyclodextrin complexes are encapsulated in fabric softener,
they are attached to the fabric in the laundry dryer.
C. Optional Ingredients
Well known optional components included in fabric conditioning
compositions are narrated in U.S. Pat. No. 4,103,047, Zaki et al.,
issued Jul. 25, 1978; for "Fabric Treatment Compositions,"
incorporated herein by reference.
Another preferred additional ingredient in the compositions herein
is free perfume, other than the perfume which is present as the
optional perfume/cyclodextrin inclusion complex, which is also very
useful for imparting the odor benefits. Such uncomplexed perfume is
preferably present at a level of from about 0.10% to about 10% by
weight of the total.
For example, perfume delivery both via free perfume and
cyclodextrin/perfume complexes, in solid, dryer-activated, fabric
conditioning compositions in laundry fabric dryers is desirable in
two ways. Product malodors can be covered by the addition of free
perfume to the softener composition to obtain a more preferred
product odor, and complexed perfume can be transferred onto fabric
with the softener actives in the laundry fabric dryer to provide
better in-wear fabric odor. (Preferably, such uncomplexed perfume
comprises at least about 1%, more preferably at least about 10% by
weight of said uncomplexed perfume, of substantive perfume
materials.)
Products of this invention preferably only contain enough free
perfume to deliver both an acceptably low product perfume odor and
an acceptable initial fabric perfume odor. Perfume incorporated
into the product in the form of perfume/CD complex as part of a
substrate article or in the form of solid fabric softener particles
containing perfume/CD complex (in the case of detergent compatible
products), will be released when the fabric is used in situations
where renewed perfume odor is really and appropriately needed,
e.g., when some moisture is present, such as when using wash cloths
and towels in a bathroom, or when there is perspiration odor on
clothes during and after a high level of physical activity.
Laundry products can also contain only the optional perfume/CD
complex, without any noticeable amount of free perfume. In this
case, the products function initially almost as unscented
products.
If a product contains both free and complexed perfume, the escaped
perfume from the complex contributes to the overall perfume odor
intensity, giving rise to a longer lasting perfume odor
impression.
Thus, by adjusting the levels, of free perfume and perfume/CD
complex it is possible to provide a wide range of unique perfume
profiles in terms of timing. (release) and/or perfume identity
(character). Solid, dryer-activated fabric conditioning
compositions are a uniquely desirable way to apply the
cyclodextrins, since they are applied at the very end of a fabric
treatment regimen when the fabric is clean and when there are
almost no additional treatments that can remove the
cyclodextrin.
All percentages, ratios, and parts herein, in the Specification,
Examples, and claims, are by weight and approximations unless
otherwise stated.
The following are nonlimiting examples of the instant articles and
methods.
Uncomplexed Normal Cyclodextrin
Uncomplexed .beta.-cyclodextrin is obtained from American
Maize-Products Company. Particle size distribution analysis is
determined using a Malvern Particle and Droplet Sizer, Model 2600C,
sold by Malvern Instruments, Inc., Southborough, Mass. It is found
that about 95% of this material has a particle size larger than 12
microns, with about 58% of the particles having a size in the 49 to
118 micron range.
Uncomplexed Cyclodextrin with Small Particle Size
The .beta.-cyclodextrin sample obtained from American-Maize
Products Company is ground in a Trost Air Impact Pulverizer jet
mill (Research Model Gem-T), sold by Garlock, Inc., Newtown, Pa.
After one pass through the jet mill, the particle size of the
ground cyclodextrin is determined by Malvern Particle and Droplet
Sizer, Model 2600C. It is found that practically the whole sample
has a particle size of about 6 microns or smaller, with about 95%
of the sample having a particle size of about 5 microns or
smaller.
Two different perfumes used in the following Examples are as
follows:
______________________________________ Relatively Nonsubstantive
Perfume (A) Substantive Perfume (B) Component Wt. % Component Wt. %
______________________________________ Alpha Pinene 5.0 Benzyl
Acetate 5.0 Cedarwood Terpenes 20.0 Benzyl Salicylate 10.0 Dihydro
Myrcenol 10.0 Coumarin 5.0 Eugenol 5.0 Ethyl Maltol 5.0 Lavandin
15.0 Ethylene Brassylate 10.0 Lemon Oil CP 10.0 Galaxolide .RTM.
(50%) 15.0 Orange Terpenes 15.0 Hexyl Cinnamic 20.0 Phenyl Ethyl
Alcohol 20.0 Aldehyde Total 100.0 Gama Methyl Ionone 10.0 Lilial
.RTM. 15.0 Patchouli 5.0 Total 100.0
______________________________________
Complex 1--Perfume A/.beta.-CD
A mobile slurry is prepared by mixing about 1 kg of .beta.-CD and
about 500 ml of water in a stainless steel mixing bowl of a
KitchenAid mixer using a plastic coated heavy-duty mixing blade.
Mixing is continued while about 176 g of Perfume A is slowly added.
The liquid-like slurry immediately starts to thicken and becomes a
creamy paste. Stirring is continued for about 30 minutes. About 500
ml of water is added to the paste and blended well. Stirring is
then resumed for an additional approximately 30 minutes. During
this time the complex again thickens, although not to the same
degree as before the additional water is added. The resulting
creamy complex is freeze-dried to produce about 1100 g of powdery
solid. Particle size distribution, including agglomerates,
determined by the Malvern Particle and Droplet Sizer, Model 2600C,
shows that about 92% of the complex powder has a size of about 11.1
microns, or less, and about 68% of the complex powder has a
particle size of about 5.3 microns, or less. Examination of the
complex particles by scanning electron microscopy shows that
practically all of the ultimate (primary) particles of the complex
have particle sizes less than about 5 microns.
Complex 2
Perfume B/.beta.-CD complex is prepared by the process of Complex
1.
______________________________________ Composition Examples
Comparative Components Example 1 Example 2
______________________________________
Ditallowalkyldimethylammonium 31.5 31.5 methyl sulfate (DTDMAMS)
Sorbitan Monostearate 31.5 31.5 Uncomplexed .beta.-cyclodextrin,
35.0 -- small-particle-size Uncomplexed normal .beta.-cyclodextrin
-- 35.0 Calcium bentonite clay 2.0 2.0 Totals 100.0 100.0
______________________________________
EXAMPLE 1
Preparation of the Coating Mix
An approximately 200 gram batch of the coating mix is prepared as
follows. An amount of about 63 g of ditallowalkyldimethylammonium
sulfate (DTDMAMS) (Sherex Chemical Co.) and about 63 g of sorbitan
monostearate (Mazer Chemicals, Inc.) are melted together at about
80.degree. C. The calcium bentonite clay (about 4 g of Bentolite L,
available from Southern Clay Co.) is slowly added to the mixture
with high shear mixing. During the mixing, the mixture is kept
molten in a boiling water bath. The uncomplexed, ground,
small-particle-size cyclodextrin (about 70 g) is then slowly added
to the mixture with high shear mixing, and the formula is mixed
until the mixture is smooth and homogenous.
Preparation of Fabric Conditioning Sheets
The coating mixture is applied to preweighed nonwoven substrate
sheets of about 9 inch.times.11 inch (approximately 23 cm.times.28
cm) dimensions. The substrate sheets are comprised of about 70%
3-denier, 19/16 inch (approximately 4 cm) long rayon fibers with
about 30% polyvinyl acetate binder. The substrate weight is about
16 g per square yard (about 1.22 g/sheet). A small amount of
formula is placed on a heated metal plate with a spatula and then
is spread evenly with a wire metal rod. A nonwoven sheet is placed
on the metal plate to absorb the coating mixture. The sheet is then
removed from the heated metal plate and allowed to cool to room
temperature so that the coating mix can solidify. The sheet is
weighed to determine the amount of coating mixture on the sheet.
The target coating is 4.0 g per sheet. If the weight is in excess
of the target weight, the sheet is placed back on the heated metal
plate to remelt the coating mixture and remove some of the excess.
If the weight is under the target weight, the sheet is also placed
on the heated metal plate and more coating mixture is added.
COMPARATIVE EXAMPLE 2
The coating mix preparation and the making of the fabric
conditioning sheets are similar to those in Example 1, except that
the uncomplexed normal cyclodextrin is used instead of the
uncomplexed, ground, small-particle-size cyclodextrin.
Fabric Treatment
Three laundry loads containing the same composition of garments,
each load including a 50/50 poly/cotton pillow case, are washed in
three automatic washers with unscented TIDE.RTM. detergent. The wet
laundry loads are transferred to, and dried in, three electric
tumble dryers with, respectively, a fabric conditioning sheet of
Example 1; a fabric conditioning sheet of Comparative Example 2;
and without any fabric conditioning sheet. After drying, the three
pillow cases from the three laundry loads are hung in a recreation
room full of tobacco odor. After about 30 minutes, the pillow case
treated with the fabric conditioning sheet of Example 1 has
noticeably less tobacco odor than the pillow case treated with the
fabric conditioning sheet of Comparative Example 2 or the pillow
case which is not treated with any fabric conditioning sheet. Flat
woven fabric materials such as pillow cases or shirt fabrics show
the most noticeable benefit. Textured fabrics, such as cotton
terries, show less benefit. It is believed that this occurs because
textured fabrics have more untreated areas which do not provide the
benefit.
______________________________________ Comparative Components
Example 3 Example 4 ______________________________________ DTDMAMS
17.2 17.2 Sorbitan monostearate 17.2 17.2 Octadecyldimethylamine
10.0 10.0 C.sub.16-18 fatty acids 17.6 17.6 Uncomplexed
.beta.-cyclodextrin, 35.0 -- small-particle-size Uncomplexed,
normal -- 35.0 .beta.-cyclodextrin Calcium bentonite clay 3.0 3.0
Totals 100.0 100.0 ______________________________________
EXAMPLE 3
A first blend of about 10 parts octadecyldimethylamine (Ethyl
Corporation) and about 17.6 parts C.sub.16-18 fatty acid (Emery
Industries, Inc.) are melted together at 80.degree. C., and a
second blend of about 17.2 parts sorbitan monostearate (Mazer
Chemicals, Inc.) and about 17.2 parts ditallowalkyldimethylammonium
methylsulfate, DTDMAMS, (Sherex Chemical Co.). are melted together
to form the softener component of the composition, during which
time the mixture is kept molten in a boiling water bath. The
calcium bentonite clay (about 3 parts Bentolite L, available from
Southern Clay Co.) is then slowly added to the mixture while high
shear mixing. An amount of about 35 parts of uncomplexed, ground,
small-particle-size .beta.-cyclodextrin is then added in small
portions and the formula is mixed until the mixture is smooth and
completely homogenous.
The coating mixture is applied to preweighed nonwoven substrate
sheets as in Example 1. The target coating is 4 g per sheet. Each
sheet contains about 2.48 g of softener, about 0.12 g of clay, and
about 1.4 g of .beta.-cyclodextrin.
COMPARATIVE EXAMPLE 4
The softener mixture of Comparative Example 4 is prepared similarly
to that of Example 3. However, the coating mixture of Comparative
Example 4 contains uncomplexed, normal .beta.-cyclodextrin instead
of the uncomplexed, ground, small-particle-size
.beta.-cyclodextrin.
Fabric Treatment
Three laundry loads containing the same composition of garments,
each load including a 50/50 poly/cotton pillow case, are washed in
three automatic washers with unscented TIDE.RTM. detergent. The wet
laundry loads are transferred to, and dried in, three electric
tumble dryers with, respectively, a fabric conditioning sheet of
Example 3; a fabric conditioning sheet of Comparative Example 4;
and without any fabric conditioning sheet. After drying, the three
pillow cases from the three laundry loads are hung in a recreation
room full of tobacco odor. After about 30 minutes, the pillow case
treated with the fabric conditioning sheet of Example 3 has
noticeably less tobacco odor than the pillow case treated with the
fabric conditioning sheet of Comparative Example 4 or the pillow
case which is not treated with any fabric conditioning sheet.
______________________________________ Components Example 5 Example
6 ______________________________________ DTDMAMS 17.2 17.3 Sorbitan
monostearate 17.2 17.3 Octadecyldimethylamine 10.0 10.0 C.sub.12-14
fatty acid 7.6 -- C.sub.16-18 fatty acid 10.0 17.0 Uncomplexed
.beta.-cyclodextrin, 20.0 16.7 small-particle-size Complex 1 --
16.7 Complex 2 15.0 -- Free Perfume B -- 1.7 Calcium bentonite clay
3.0 3.3 Totals 100.0 100.0
______________________________________
EXAMPLE 5
A first blend of about 10 parts octadecyldimethylamine (Ethyl
Corporation), about 7.6 parts C.sub.12-14 fatty acid and about 10
parts of C.sub.16-18 fatty acid (Emery Industries, Inc.) are melted
together at about 80.degree. C., and a second blend of about 17.2
parts sorbitan monostearate (Mazer Chemicals, Inc.) and about 17.2
parts ditallowalkyldimethylammonium methylsulfate, DTDMAMS, (Sherex
Chemical Co.) are melted together to form the softener component of
the composition, during which time the mixture is kept molten in a
boiling water bath. The calcium bentonite clay (about 3 parts
Bentolite L, available from Southern Clay Co.) is then slowly added
to the mixture while high shear mixing. An amount of about 35 parts
mixed cyclodextrin/cyclodextrin complex (about 20 parts of
uncomplexed, ground, small-particle-size .beta.-cyclodextrin and
about 15 parts of Complex 2) are then added in small portions and
the formula is mixed until the mixture is smooth and completely
homogenous.
The coating mixture is applied to preweighed nonwoven substrate
sheets as in Example 1. The target coating is 4 g per sheet. Each
sheet contains about 2.48 g of softener, about 0.12 g of clay, and
about 1.4 g of .beta.-cyclodextrin and .beta.-cyclodextrin/perfume
inclusion complex mixture.
EXAMPLE 6
A dryer-added fabric conditioning article comprising a rayon
nonwoven fabric substrate [having a weight of about 1.22 g per 99
sq. in. (approximately 639 cm.sup.2)] and a fabric conditioning
composition is prepared in the following manner.
A premixture is prepared by admixing about 10 parts
octadecyldimethylamine with about 17 parts C.sub.16-18 fatty acid
at about 75.degree. C. Then about 17.3 parts sorbitan monostearate
and about 17.3 parts ditallowalkyldimethylammonium methylsulfate
are added with high shear mixing at about 75.degree. C. After the
addition is completed and a sufficient period of mixing time has
elapsed, about 3.3 parts of Bentolite L particulate clay is added
slowly while maintaining the high shear mixing action. Then about
16.7 parts of uncomplexed, ground, small-particle-size .beta.-CD
and about 16.7 parts of Complex 1 are added with mixing. Finally
about 1.7 parts of free Perfume B is added to complete the
preparation of the fabric conditioning composition.
The flexible substrate, comprised of about 70% 3-denier, 19/16 inch
long (approximately 4 cm) rayon fibers and about 30% polyvinyl
acetate binder, is impregnated by coating one side of a continuous
length of the substrate and contacting it with a rotating
cylindrical member which serves to press the liquified mixture into
the interstices of the substrate. The amount of fabric conditioning
mixture applied is controlled by the flow rate of the mixture
and/or the line speed of the substrate. The substrate is passed
over several chilled tension rolls which help solidify the
conditioning mixture. The substrate sheet is about 9 inches wide
(approximately 23 cm) and is perforated in lines at about 11 inch
intervals (approximately 28 cm) to provide detachable sheets. Each
sheet is cut with a set of knives to provide three evenly spaced
parallel slits averaging about 4 inches in length (approximately 10
cm). In this Example 6, the application rate is adjusted to apply
about 3 g of coating mixture per sheet. Each sheet contains about
1.85 g of softener, about 0.1 g of clay, about 0.5 g of .beta.-CD,
and about 0.5 g of Complex 3, and about 0.05 g of free Perfume
B.
Shirts treated in tumble dryer with a sheet of either Example 5 or
Example 6 and worn by a constant cigarette smoker have noticeably
lower tobacco odor than shirts that are not treated.
______________________________________ Examples of
Detergent-Compatible Particles Softener Core Particles Components
Example 7 Example 8 ______________________________________
Ditallowalkyldimethylammonium 38.51 38.51 methylsulfate (DTDMAMS)
Cetyl alcohol 19.17 19.17 Sorbitan monostearate 19.17 19.17
Uncomplexed, ground, 20.15 10.15 small-particle-size .beta.-CD
Complex 1 -- 10.00 Calcium bentonite clay 3.00 3.00 Totals 100.00
100.00 ______________________________________
EXAMPLE 7
The DTDMAMS, cetyl alcohol and sorbitan monostearate are blended
together in a PVM 40 Ross mixer (Charles Ross & Sons Company,
Hauppauge, N.Y.) at about 71.degree. C. The molten "triblend" is
then mixed for about one hour. At the end of one hour, the
temperature is raised to about 79.degree.-85.degree. C. under
vacuum (about 330-430 mm Hg). When the temperature has stabilized
in this range, the Ross anchor and disperser are turned on and the
cyclodextrin and the clay are added, the mixture is blended for
about 5 minutes and then sheared with the Ross colloid mixer for
about 10 minutes. The softener composition is then poured into
trays and cooled overnight at about 4.degree. C. Particles are
formed by cooling and then milling in a Fitzmill, Model DA506 (The
Fitzpatrick Company, Elmhurst, Ill.) at 4740 rpm's through a 4 mesh
screen. The particles are then sized through 11 on 26 (U.S.
Standard screens, (0.6-1.7 mm) particle size).
The particles are then coated with a 10% solution of Ethocel in
methanol. The coating is applied in an 18 inch Wurster Coater
(Coating Place, Inc., P.O. Box 248, Verona, Wis.). The ethyl
cellulose used is Ethocel Std. 10 (Dow Chemical Co., Midland,
Mich.), which has an Ubbelohde viscosity of about 9.0-11.0,
measured at 25.degree. C. as a 5% solution in 80% toluene/20%
ethanol.
The following conditions are used to apply the cellulose-based
coating:
______________________________________ Fluidizing Air 15.8
Cu.M/min. at 40.5.degree. C. Atomizing Air Volume 0.37 Cu.M/min.
Atomizing Air Rate 5624 g/sq.cm. Inlet Air Temperature 38.degree.
C.-43.degree. C. Outlet Air Temperature 30.degree. C.-32.degree. C.
Pump Rate 0.2 Kg/min. Nozzle Size CPI-18-A74* Partition Gap 216 mm
.times. 267 mm Partition Size 19 mm Run Time 55 min.
______________________________________ *Available from Coating
Place, Inc.
The amount of coating applied to the particles is about 3% by
weight of the total coated particle weight. When the coating is
completed, the softener particles are resized through 11 on 26 mesh
U.S. Standard screens and are then ready for use "as is" or for
blending into detergent granules.
EXAMPLE 8
Softener particles of Example 8 are prepared similarly to the
particles of Example 7, with the exception that the mixture of
uncomplexed .beta.-CD and Complex 1 is used in place of all
uncomplexed .beta.-CD.
EXAMPLE 9
A detergent/softener composition is prepared by mixing about 5.2
parts of the coated softener particles of Example 7 with about 94.8
parts of the following granular detergent composition:
______________________________________ Ingredient Parts
______________________________________ Na C.sub.13 linear alkyl
benzene sulfonate 9.5 Na C.sub.14 -C.sub.l5 fatty alcohol sulfate
9.5 Ethoxylated C.sub.12 -C.sub.l3 fatty alcohol 1.9 Na.sub.2
SO.sub.4 11.1 Sodium silicate (1.6r) 6.5 Polyethylene glycol (M.W.
8,000) 0.7 Polyacrylic acid (M.W 1,200) 0.9 Sodium tripolyphosphate
31.0 Sodium pyrophosphate 7.5 Na.sub.2 CO.sub.3 10.2 Optical
brightener 0.2 Protease enzyme (Alcalase) 0.7 Moisture 9.3 Free
Perfume B 1.0 Total 100.0
______________________________________
EXAMPLE 10
Alternate granular detergent/softener compositions are prepared by
mixing about 5.2 parts of the coated softener of Example 8 with
about 94.8 parts of the following granular detergent
composition:
______________________________________ Ingredient Parts
______________________________________ Na C.sub.13 linear alkyl
benzene sulfonate 11.5 Na C.sub.14 -C.sub.15 fatty alcohol sulfate
11.5 Ethoxylated C.sub.12 -C.sub.13 fatty alcohol 1.9 Na.sub.2
SO.sub.4 14.0 Sodium silicate (1.6r) 2.3 Polyethylene glycol (M.W.
8,000) 1.8 Polyacrylic acid (M.W. 1,200) 3.5 Hydrated Zeolite A (-2
microns) 28.9 Na.sub.2 CO.sub.3 17.0 Optical brightener 0.2
Protease enzyme (Alcalase) 0.6 Perfume B 1.0 Moisture and
Miscellaneous 5.8 Total 100.0
______________________________________
* * * * *